CN113916845A - Method for detecting polyhydroxy compound - Google Patents
Method for detecting polyhydroxy compound Download PDFInfo
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- CN113916845A CN113916845A CN202010662997.2A CN202010662997A CN113916845A CN 113916845 A CN113916845 A CN 113916845A CN 202010662997 A CN202010662997 A CN 202010662997A CN 113916845 A CN113916845 A CN 113916845A
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Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention discloses a method for detecting polyhydroxy compounds, which provides a graphene oxide quantum dot solution; mixing and reacting the graphene oxide quantum dot solution with a boric acid derivative to obtain a first mixed solution; and mixing the first mixed solution with a sample to be detected, and then carrying out quantitative detection on the polyhydroxy compound in the sample to be detected by adopting a fluorescence spectrophotometry. According to the invention, the graphene oxide quantum dots modified by the boric acid derivative in the first mixed solution are obtained as the fluorescent marker by modifying the graphene oxide quantum dots by the boric acid derivative, and the method for detecting the polyhydroxy compound by using the fluorescence spectrophotometry has good selectivity and higher sensitivity, and can meet the requirement of accurately, quickly and sensitively detecting the polyhydroxy compound under different environments.
Description
Technical Field
The invention relates to the technical field of detection of hydroxyl compounds, in particular to a method for detecting a polyhydroxy compound.
Background
The size of the graphene quantum dot is generally 10-100 nm, and the graphene quantum dot has wide application in many aspects such as fluorescence and electrochemical luminescence sensors, cell imaging and the like due to the wide absorption range, excellent light stability, good biocompatibility and extremely low cytotoxicity. However, since the application of the graphene quantum dots in fluorescence detection is often limited by the low fluorescence quantum yield, additional difficulties are brought to the preparation of the graphene quantum dot fluorescence sensing system with good selectivity and sensitivity.
Polyhydroxy compounds are important organic compounds in nature, and have irreplaceable modification effect on water-soluble quantum dots due to good hydrophilicity. At present, there are various methods for detecting whether there is a residue after modifying quantum dots, wherein electrochemical methods are among the most widely studied methods. Most electrochemical detection methods use a specific oxidase as the core of the detection means, which makes the electrochemical means expensive and sensitive to the detection environment.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for detecting polyhydroxy compounds, which aims to solve the problem of poor selectivity of the existing method for detecting polyhydroxy compounds.
The technical scheme of the invention is as follows:
a method for detecting a polyhydroxy compound, comprising the steps of:
providing a graphene oxide quantum dot solution;
mixing and reacting the graphene oxide quantum dot solution with a boric acid derivative to obtain a first mixed solution;
and mixing the first mixed solution with a sample to be detected, and then carrying out quantitative detection on the polyhydroxy compound in the sample to be detected by adopting a fluorescence spectrophotometry.
Has the advantages that: according to the invention, the graphene oxide quantum dots modified by the boric acid derivative in the first mixed solution are obtained as the fluorescent marker by modifying the graphene oxide quantum dots by the boric acid derivative, and the method for detecting the polyhydroxy compound by using the fluorescence spectrophotometry has good selectivity and higher sensitivity, and can meet the requirement of accurately, quickly and sensitively detecting the polyhydroxy compound under different environments.
Drawings
FIG. 1 is a flow chart of a method for detecting a polyhydroxy compound in accordance with an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a cross-linking molecule formed by cross-linking lactose and the sulfanilic acid-modified graphene oxide quantum dots in the embodiment of the present invention.
Detailed Description
The present invention provides a method for detecting a polyhydroxy compound, and the present invention is further described in detail below in order to make the objects, technical solutions, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, an embodiment of the present invention provides a method for detecting a polyol, including the steps of:
s10, providing a graphene oxide quantum dot solution;
s20, mixing and reacting the graphene oxide quantum dot solution and a boric acid derivative to obtain a first mixed solution;
and S30, mixing the first mixed solution with a sample to be detected, and then carrying out quantitative detection on the polyhydroxy compound in the sample to be detected by adopting a fluorescence spectrophotometry.
In the embodiment, the boric acid derivative is used for modifying the graphene oxide quantum dots, so that the fluorescence quantum yield of the graphene quantum dots is improved; meanwhile, the boric acid derivative modified graphene oxide quantum dots are crosslinked with the polyhydroxy compound to cause the modified graphene oxide quantum dots to agglomerate or form rigid structure molecules, when the modified graphene oxide quantum dots agglomerate due to crosslinking, the fluorescence of the boric acid derivative modified graphene oxide quantum dots is quenched, and when the modified graphene oxide quantum dots are promoted to form the rigid structure molecules due to crosslinking, the fluorescence of the boric acid derivative modified graphene oxide quantum dots is enhanced. Therefore, in the embodiment, the graphene oxide quantum dots are modified by the boric acid derivative, so that the graphene oxide quantum dots modified by the boric acid derivative in the first mixed solution are obtained as the fluorescent marker, and the method for detecting the polyhydroxy compound by using the fluorescence spectrophotometry has good selectivity and high sensitivity; meanwhile, the detection method can realize accurate, rapid and sensitive detection of the polyhydroxy compound under different environments.
Specifically, the surfaces of the graphene oxide quantum dots are provided with a large amount of negative charges, and the negative charges enable the graphene quantum dots to be mutually repelled, so that mutual collision and fluorescence quenching caused by energy transfer are prevented; the boric acid derivative is used for modifying the graphene oxide quantum dots, so that the fluorescence quantum yield of the graphene oxide quantum dots can be improved; after the polyhydroxy compound is added, polyhydroxy compounds with different structures and boric acid derivatives form a cross-linked structure through covalent bonds to cause fluorescence quenching or enhancement of the boric acid derivative modified graphene oxide quantum dots (polyhydroxy compounds (such as monosaccharide) with rigid structures tend to be cross-linked with a plurality of boric acid derivative modified graphene oxide quantum dots to cause fluorescence quenching of the plurality of boric acid derivative modified graphene oxide quantum dots due to agglomeration, polyhydroxy compounds (such as double ponds) with flexible structures tend to be cross-linked with a single boric acid derivative modified graphene oxide quantum dot to form rigid molecules, so that the fluorescence enhancement caused by energy loss caused by chemical bond rotation in the boric acid derivative modified graphene oxide quantum dots is effectively inhibited, and the specific detection of the polyhydroxy compounds with different structures is realized, i.e. good selectivity for polyol detection.
In one embodiment, in step S10, the graphene oxide quantum dot solution is obtained by dissolving graphene oxide quantum dots in water, and the concentration of the graphene oxide quantum dot solution is 10 to 30 mg/mL; for example, the concentration is 10mg/mL, 12mg/mL, 15mg/mL, 25mg/mL, or the like. Within the concentration range, the boric acid derivative can react with the graphene oxide quantum dots, so that the boric acid derivative modifies the graphene oxide quantum dots.
In one embodiment, in the graphene oxide quantum dot solution, the molecular weight of the graphene oxide quantum dots is 3000-5000 Da (for example, 3000Da, 3500Da, 4000Da, 4200Da, etc.); and/or the lateral dimension of the graphene oxide quantum dots is 3-5 nm (for example, the lateral dimension is 3nm, 3.2nm, 3.3nm, 3.8nm, etc.); and/or the thickness of the graphene oxide quantum dots is 2-4 nm (such as 2nm, 2.4nm, 2.5nm and 2.9 nm); and/or the number of layers of the graphene oxide quantum dots is 3-6 (for example, the number of layers is 3, 4, 5, 6). The graphene oxide quantum dots contain a large number of carboxyl groups, hydroxyl groups and epoxy groups, for example, the edges of the graphene oxide quantum dots contain a large number of carboxyl groups and hydroxyl groups.
In one embodiment, in step S20, the boric acid derivative may be selected from, but not limited to, at least one of o-aminobenzeneboronic acid, m-aminobenzeneboronic acid, p-aminobenzeneboronic acid, o-chlorobenzeneboronic acid, m-chlorobenzeneboronic acid, p-chlorobenzeneboronic acid, o-hydroxyphenylboronic acid, m-hydroxyphenylboronic acid, p-hydroxyphenylboronic acid, o-carboxyphenylboronic acid, m-carboxyphenylboronic acid, and p-carboxyphenylboronic acid. The boric acid derivative modified by the boric acid derivative and the graphene oxide quantum dot obtained by the reaction has higher fluorescence quantum yield, and is favorable for improving the sensitivity of the boric acid derivative modified graphene oxide quantum dot as a fluorescence marker to the detection of polyhydroxy compounds.
In one embodiment, in step S20, the mass ratio of the graphene oxide quantum dots to the boric acid derivative is 1:0.01 to 0.1. For example, the mass ratio of the graphene oxide quantum dots to the boric acid derivatives may be 1:0.02, 1:0.047, 1:0.075, 1:0.012, or the like.
In a further embodiment, in step S20, the step of mixing and reacting the graphene oxide quantum dot solution with a boric acid derivative includes: in the presence of a carbodiimide compound, mixing and reacting the graphene oxide quantum dot solution with a boric acid derivative; the carbodiimide compound may be selected from, but not limited to, at least one of 1- (3-Dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (1- (3-dimethylamino propyl) -3-ethylcarbodiimide hydrochloride, EDC. HCl), dicyclohexylcarbodiimide, and N, N' -diisopropylcarbodiimide. The carbodiimide compound has an activation effect on reactive groups such as carboxyl groups on the graphene oxide quantum dots, and is beneficial to the reaction of the boric acid derivative and the graphene oxide quantum dots, so that the boric acid derivative is beneficial to modifying the graphene oxide quantum dots.
In a further embodiment, in step S20, the mass ratio of the graphene oxide quantum dots, the boric acid derivative, and the carbodiimide compound is 1:0.01 to 0.1:0.02 to 0.04. For example, the mass ratio of the graphene oxide quantum dots, the boric acid derivative, and the carbodiimide compound may be 1:0.02:0.08, 1:0.047:0.02, 1:0.075:0.033, 1:0.012:0.024, or the like. In the mass ratio range, the boric acid derivative modified graphene oxide quantum dots obtained by the reaction have higher fluorescence quantum yield, and the sensitivity of the boric acid derivative modified graphene oxide quantum dots serving as fluorescent markers to the detection of polyhydroxy compounds is favorably improved.
In one embodiment, in step S20, the temperature of the reaction is 2 to 8 ℃ (for example, the temperature can be 2 ℃, 4 ℃, 5 ℃, 8 ℃ and the like); and/or the reaction time is 10-60 min (for example, the reaction time can be 20min, 25min, 30min, 40min, and the like).
In one embodiment, in step S30, the polyol may be a monosaccharide or a disaccharide.
Further in one embodiment, the polyol is a monosaccharide that may be glucose, fructose, galactose or mannose and the disaccharide may be lactose or sucrose; but is not limited thereto. Preferably, the monosaccharide is glucose.
Specifically, when the boric acid derivative is sulfanilic acid, the carbodiimide compound is EDC & HCl, and the polyhydroxy compound is monosaccharide (the number of hydroxyl groups in a molecule is less than or equal to 5), the monosaccharide molecules are small, the molecules are in short and small plane rigid structures, and the molecules cannot be bent to be combined with a plurality of sulfanilic acid compounds on one graphene oxide quantum dot, for example, the polyhydroxy compound is glucose (the structure is glucose)
) In the process, the reaction formula of modifying the graphene oxide quantum dots by the aminobenzene boric acid is as follows:
the reaction formula for crosslinking the aminobenzoic acid modified graphene oxide quantum dots and glucose is as follows:
because the glucose contains two pairs of opposite trans-ortho-hydroxyl groups, a single glucose molecule is mainly prone to be combined with a plurality of (more than 2) modified graphene oxide quantum dots, so that the modified graphene oxide quantum dots are agglomerated, and the fluorescence of the modified graphene oxide quantum dots is quenched to the maximum extent; other monosaccharide substances only can be connected with the less modified graphene oxide quantum dots because the monosaccharide substances do not contain two pairs of opposite trans-ortho-hydroxyl groups, so that the fluorescence of the partially modified graphene oxide quantum dots is quenched; it is known that this detection method has a higher detection sensitivity for glucose than other monosaccharide substances, and therefore, it is preferable that the monosaccharide is glucose. For the disaccharide, the disaccharide has larger molecules, the molecules have long and flexible structures, and the molecules have more ortho-hydroxyl pairs (the number of hydroxyl groups in the molecules is more than or equal to 8 and less than or equal to 10), so that the disaccharide is more prone to be combined with aminobenzene boric acid on a single graphene oxide quantum dot to form a larger planar structure; for example, when the polyol is lactose (structure
) In this case, the modified graphene oxide quantum dots are converted into molecules having a rigid structure, which can effectively inhibit energy loss in the molecules due to chemical bond rotation, thereby increasing the fluorescence intensity.
In one embodiment, step S30 specifically includes:
s31, preparing N groups of polyhydroxy compound solutions with different standard concentrations, and mixing the N groups of polyhydroxy compound solutions with different standard concentrations and a sample to be detected with the first mixed solution respectively to obtain N groups of standard mixed solutions and a second mixed solution, wherein N is an integer greater than or equal to 5;
s32, performing fluorescence measurement on the N groups of standard mixed liquor and the second mixed liquor respectively, and fitting out a relational equation between the fluorescence intensity of the standard mixed liquor and the concentration of the polyhydroxy compound solution;
and S33, calculating the concentration of the polyhydroxy compound in the sample to be detected according to the relation equation and the measured fluorescence intensity of the second mixed solution.
In one embodiment, in step S31, the polyol solution is obtained by dissolving a polyol in water. And in the N groups of polyhydroxy compound solutions with different standard concentrations, water with the concentration of 0 in one group of polyhydroxy compound solution is used as a control group. The sample to be measured does not contain a substance having a fluorescent property.
In one embodiment, the sample to be tested may be a cleaning residual solution of a quantum dot system, and the quantum dot system may be a quantum dot system in which a quantum dot is modified by a polyhydroxy compound or a quantum dot system in which a polyhydroxy compound performs ligand exchange with an original ligand on the surface of a quantum dot. The quantum dots in the quantum dot system comprise at least one of II-VI family quantum dots, III-V family quantum dots and IV-VI family quantum dots; the quantum dots in the quantum dot system can be all-inorganic perovskite quantum dots, organic-inorganic perovskite quantum dots, copper-sulfur-indium ternary quantum dots or silicon quantum dots; the structure of the quantum dots in the quantum dot system can be a uniform binary component mononuclear structure, a uniform multi-component alloy component mononuclear structure, a multi-component alloy component gradient mononuclear structure, a binary component discrete core-shell structure, a multi-component alloy component discrete core-shell structure or a multi-component alloy component gradient core-shell structure; when the quantum dots in the quantum dot system are core-shell quantum dots, the core material and the shell material can be independently selected from CdSe, CdS, ZnSe, ZnS, CdTe, ZnTe, CdZnS, ZnSeS, CdSeS, CdSeSTe or CdZnSeTe of II-VI families, InP, InAs or InAsP of III-V families, PbS, PbSe, PbSeS, PbSeTe or PbSTe of IV-VI families, or any one or more of the above.
The present invention will be described in detail below with reference to specific examples.
Example 1
(1) The method provides a CdZnS water-soluble quantum dot modified by glucose, and comprises the steps of washing 3 times by distilled water and collecting the residual liquid of the 3 rd washing.
(2) The graphene oxide quantum dot aqueous solution with the concentration of 10mg/mL and the edge having a large number of carboxyl groups, the molecular weight of 3000Da, the number of layers of 3, the transverse dimension of 3nm and the thickness of 2nm is provided.
(3) And (3) mixing 1mL of the graphene oxide quantum dot aqueous solution obtained in the step (2) with 0.2mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.8mg of p-aminobenzene boric acid, and carrying out ultrasonic reaction (with ultrasonic power of 100W) at 4 ℃ for 30min to obtain a p-aminobenzene boric acid modified graphene oxide quantum dot solution.
(4) Preparing glucose solutions with standard concentrations of 0, 2, 4, 8 and 15mg/mL, respectively adding 0.5mL and 10mg/mL of p-aminobenzeneboronic acid modified graphene oxide quantum dot solutions with the same volume as the glucose solutions, and after reacting for 30min, measuring the fluorescence intensities of five groups of mixed solutions to be 5843, 4762, 3287, 1289 and 461 respectively (the fluorescence intensity measured after reacting for 30min is the same as the fluorescence intensity measured after reacting for 1min and immediately mixing); fitting to obtain a relational equation between the fluorescence intensity of the mixed solution and the concentration of the glucose solution, wherein the relational equation comprises the following steps: and y is 5189.4-349 x.
(5) And (3) adding 0.5mL of 10mg/mL aminobenzene boric acid modified graphene oxide into the residual solution (3mL) obtained in the step (1), reacting for 30min, measuring the fluorescence intensity of the mixed solution to be 5021, and substituting the fluorescence intensity into the relation equation obtained in the step (4) to obtain the concentration of the glucose in the residual solution to be 0.48 mg/mL.
Example 2
(1) Provides a PbSe water-soluble quantum dot modified by fructose, which is washed 3 times by distilled water, and the residual liquid of the 3 rd washing is collected.
(2) A graphene oxide quantum dot aqueous solution with the concentration of 12mg/mL and the edge having a large number of carboxyl groups, the molecular weight of 3500Da, 6 layers, the transverse dimension of 3.2nm and the thickness of 2.5nm is prepared and supplied.
(3) And (3) mixing 1mL of the graphene oxide quantum dot aqueous solution obtained in the step (2) with 0.4mg of dicyclohexylcarbodiimide and 0.9mg of p-chlorobenzeneboronic acid, and carrying out ultrasonic reaction (with ultrasonic power of 150W) at 2 ℃ for 40min to obtain a p-chlorobenzeneboronic acid modified graphene oxide quantum dot solution.
(4) Preparing fructose solutions with standard concentrations of 0, 2, 4, 8 and 15mg/mL, respectively adding 0.5mL and 10mg/mL parachlorophenylboronic acid modified graphene oxide quantum dot solutions which are equal in volume to the fructose solutions, and after reacting for 30min, measuring the fluorescence intensities of five groups of mixed solutions to be 5840, 4562, 3087, 1589 and 861 respectively (the fluorescence intensity measured after reacting for 30min is the same as the fluorescence intensity measured after reacting for 2min and immediately mixing); fitting to obtain a fitting relation equation between the fluorescence intensity of the mixed solution and the concentration of the fructose solution, wherein y is 5055.8-322 x.
(5) Adding 0.5mL of 10mg/mL parachlorophenylboronic acid modified graphene oxide into the residual solution (3mL) obtained in the step 1, reacting for 30min, measuring the fluorescence intensity of the mixed solution to 5032, and substituting the fluorescence intensity into the relational equation obtained in the step 4 to obtain the concentration of fructose in the residual solution, namely 0.074 mg/mL.
Example 3
(1) The InAs water-soluble quantum dots modified by lactose are cleaned for 3 times by distilled water, and then the residual liquid of the 3 rd cleaning is collected.
(2) Preparing a 15mg/mL graphene oxide quantum dot aqueous solution with the edge having a large number of hydroxyl groups, the molecular weight of 4000Da, the number of layers of 4, the transverse dimension of 3.8nm and the thickness of 2.9 nm.
(3) And (3) mixing 1mL of the aqueous solution of the graphene oxide quantum dots obtained in the step (2), 0.3m N, N' -diisopropylcarbodiimide and 0.7mg of p-carboxyphenylboronic acid, and carrying out ultrasonic reaction (with the ultrasonic power of 200W) at 5 ℃ for 25min to obtain a p-carboxyphenylboronic acid modified graphene oxide quantum dot solution.
(4) Preparing lactose solutions with standard concentrations of five groups of 0, 2, 4, 8 and 15mg/mL, respectively adding 0.5mL and 10mg/mL of p-carboxyphenylboronic acid modified graphene oxide quantum dot solutions with the same volume as the lactose solutions, and after reacting for 30min, measuring the fluorescence intensities of the five groups of mixed solutions to be 5840, 6562, 7087, 8189 and 10532 respectively (the fluorescence intensity measured after reacting for 30min is the same as the fluorescence intensity measured after reacting for 1min and immediately after mixing); the equation of the relationship between the fluorescence intensity of the mixed solution and the concentration of the lactose solution is obtained by fitting, and the equation is 5856.4+307.8 x.
(5) And (3) adding 0.5mL of 10mg/mL of p-carboxyphenylboronic acid modified graphene oxide into the residual liquid (3mL) obtained in the step (1), reacting for 30min, measuring the fluorescence intensity 6218 of the mixed solution, and substituting the fluorescence intensity into the relation equation obtained in the step (4) to obtain the concentration of the lactose in the residual liquid, namely 1.17 mg/mL.
Example 4
(1) The method provides the CdSeS @ ZnS water-soluble quantum dots modified by sucrose, and comprises the steps of washing the CdSeS @ ZnS water-soluble quantum dots for 3 times by using distilled water and collecting the residual liquid of the 3 rd washing.
(2) Preparing a 25mg/mL graphene oxide quantum dot aqueous solution with a large number of carboxyl groups on the edge, a molecular weight of 4200Da, 4 layers, a transverse size of 3.3nm and a thickness of 2.4 nm.
(3) And (3) mixing 1mL of the aqueous solution of the graphene oxide quantum dots obtained in the step (2), 0.6mg of N, N' -diisopropylcarbodiimide and 0.3mg of m-chlorobenzeneboronic acid, and carrying out ultrasonic reaction at 8 ℃ for 20min (with the ultrasonic power of 250W) to obtain a solution of the graphene oxide quantum dots modified by the m-chlorobenzeneboronic acid.
(4) Preparing five groups of sucrose solutions with standard concentrations of 0, 2, 4, 8 and 15mg/mL, respectively adding 0.5mL and 10mg/mL of m-chlorobenzeneboronic acid modified graphene oxide quantum dot solutions with the same volume as the sucrose solutions, and after reacting for 30min, measuring the fluorescence intensities of the five groups of mixed solutions to be 5840, 6362, 7487, 8069 and 11532 respectively (the fluorescence intensity measured after reacting for 30min is the same as the fluorescence intensity measured after reacting for 3min and immediately mixing); fitting to obtain a relational equation between the fluorescence intensity of the mixed solution and the concentration of the sucrose solution, wherein the relational equation comprises the following steps: y 5702.7+376.1 x.
(5) And (3) adding 0.5mL of m-chlorobenzeneboronic acid modified graphene oxide of 10mg/mL into the residual solution obtained in the step (1), reacting for 30min, measuring the fluorescence intensity of the mixed solution to be 5749, and substituting the fluorescence intensity into the relation equation obtained in the step (4) to obtain the concentration of the sucrose in the residual solution to be 0.12 mg/mL.
From the embodiments 1 to 4, the detection method of the polyhydroxy compound in the embodiments has good selectivity (that is, the phenomenon that the fluorescence effect of the graphene oxide quantum dot-based fluorescence detection system on monosaccharide and disaccharide is opposite) and high sensitivity (the detection system can be immediately detected after being mixed with the polyhydroxy compound). The lowest detection concentration of the method is 0.01 mg/mL.
In summary, the invention provides a method for detecting a polyhydroxy compound, the boric acid derivative is used for modifying graphene oxide quantum dots to obtain the graphene oxide quantum dots modified by the boric acid derivative in the first mixed solution as a fluorescent marker, and the method for detecting the polyhydroxy compound by using the fluorescence spectrophotometry has good selectivity and higher sensitivity, and can meet the requirement of accurately, quickly and sensitively detecting the polyhydroxy compound under different environments.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for detecting a polyhydroxy compound, comprising the steps of:
providing a graphene oxide quantum dot solution;
mixing and reacting the graphene oxide quantum dot solution with a boric acid derivative to obtain a first mixed solution;
and mixing the first mixed solution with a sample to be detected, and then carrying out quantitative detection on the polyhydroxy compound in the sample to be detected by adopting a fluorescence spectrophotometry.
2. The method as claimed in claim 1, wherein the step of mixing the first mixed solution with a sample to be tested and quantitatively detecting the polyhydroxy compound in the sample to be tested by fluorescence spectrophotometry comprises:
preparing N groups of polyhydroxy compound solutions with different standard concentrations, and mixing the N groups of polyhydroxy compound solutions with different standard concentrations and a sample to be detected with the first mixed solution respectively to obtain N groups of standard mixed solutions and a second mixed solution, wherein N is an integer more than or equal to 5;
respectively carrying out fluorescence measurement on the N groups of standard mixed liquor and the second mixed liquor, and fitting out a relation equation between the fluorescence intensity of the standard mixed liquor and the concentration of the polyhydroxy compound solution;
and calculating the concentration of the polyhydroxy compound in the sample to be detected according to the relation equation by using the measured fluorescence intensity of the second mixed solution.
3. The detection method according to claim 1, wherein the concentration of the graphene oxide quantum dot solution is 10-30 mg/mL.
4. The detection method according to claim 3, wherein in the graphene oxide quantum dot solution, the molecular weight of the graphene oxide quantum dots is 3000-5000 Da; and/or the lateral size of the graphene oxide quantum dots is 3-5 nm; and/or the thickness of the graphene oxide quantum dots is 2-4 nm; and/or the number of layers of the graphene oxide quantum dots is 3-6.
5. The detection method according to claim 1, wherein the boric acid derivative is at least one selected from the group consisting of o-aminobenzeneboronic acid, m-aminobenzeneboronic acid, p-aminobenzeneboronic acid, o-chlorobenzeneboronic acid, m-chlorobenzeneboronic acid, p-chlorobenzeneboronic acid, o-hydroxyphenylboronic acid, m-hydroxyphenylboronic acid, p-hydroxyphenylboronic acid, o-carboxyphenylboronic acid, m-carboxyphenylboronic acid and p-carboxyphenylboronic acid.
6. The detection method according to claim 1, wherein the step of mixing and reacting the graphene oxide quantum dot solution with the boric acid derivative comprises: in the presence of a carbodiimide compound, mixing and reacting the graphene oxide quantum dot solution with a boric acid derivative; the carbodiimide compound is at least one selected from the group consisting of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide and N, N' -diisopropylcarbodiimide.
7. The detection method according to claim 6, wherein the mass ratio of the graphene oxide quantum dots, the boric acid derivative and the carbodiimide compound is 1:0.01 to 0.1:0.02 to 0.04.
8. The detection method according to claim 1, wherein the reaction temperature is 2 to 8 ℃; and/or; the reaction time is 10-60 min.
9. The detection method according to claim 1, wherein the polyol is a monosaccharide or a disaccharide.
10. The method according to claim 9, wherein the monosaccharide is glucose, fructose, galactose or mannose, and the disaccharide is lactose or sucrose.
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